Process of refining mineral oils



M. TEPLITZ .April 14, 1931.

PROCESS OF REFINING MINERAL OILS Filed Nov. 18

All.

SQ EN m Patented Apr. 14, 19731`v` UNITED STATES PATENT] OFFICE IOBRIS TEPLITZ, OF KANSAS CITY, MISSOURI, ASSIGNOR T0 CORONA CONVERSION COB- '.POBATION, OF KANSAS'CITY, MISSOURI, A CORPORATION 0F ARIZONA Pnocnss or REFINING MINERAL oILs application nea november 1s, 1925. serial no. 69,917.

This invention relates to processes of rening mineral oils; and it'has to do more particularly with the relining of mineral oils which are characterized by a substantial content of gum-forming unsaturates, often in company with impurities, such as sulfur, causing poor color and disagreeable odor. The invention is concerned especially with the treatment of cracked hydrocarbon distillates, particularly cracked gasolines, which often containl -orming olens or other unsaturates, su fur, and the like.

As the invention is of greatest present utility in the treatment of cracked hydrocarbon motor fuels derived from petroleum or other mineraly oils'b so-called cracking or converting metho s of various kinds, that phase ofthe invention will be more articularly referred lto hereinafter .in exp aining the principles :upon which the invention rests.

This is not to be understood, however, asintended toV limit the scope of the invention which is of general applicability to the reof mineral oils.

as been the practice heretofore to treat Vdoctor test for sulfur.

gasolines and other mineral oil distillates, where these contain substantial proportions of unsaturated compounds, especially those of gum-forming properties, with strong sulfuric acid to remove such compounds as a sludge. Such methods of treatment, -involving not only treatment with acid but also .subsequent treatments with alkali, washing,

etc., to bring the product to good color and odor, and to the necessary degree of neutrality, are not only troublesome and expensive to carry out but they also occasion considerable loss oi the gasoline or other distillate treated. lt is one o the principal objects of the present invention to enable mineral oils, particularly gasolines and other petroleum distillates, to be refined and brought to a condition of good color and stability while avoiding the diiiiculties and losses characterizing the refining methods ofthe prior art.

Generally described, the process of the present invention comprises rst chlorinating the mineral oil to be refined by means of a suitable chlorinating agent which may be either r'e Chlorine or a compound containing indetail as an illustrative example, reference being also had to the accompanying drawing which shows in side elevatlon, more or less diagrammatically, suitable apparatus which maybe used in carryinglout the process.

In the typical embodiment of the new process to be described by way of example, 1t will be assumed that the mineral oil to be rened 'is a cracked mineral oil distillate of about 52 B. gravity, containing in the neighborhood of 12 per cent of oleins by the usual methods of estlmation and giving a positive The color of this crude distillate is a canary yellow. A quantity'of this distillate to be rened is run intov a suitable tank or other container (not shown) and chlorin as is passed into it until the color begins to arken perceptibly, indiating, in the case of this particular distillate,

that a suiiicient amount of chlorin has been bubbled through to eiect chlorination to the desired extent. A further quantity of chlorin may be passed into the distillate as a precautionary measure, but ordinarily this will be found unnecessar The gasoline t us chlorinated is next 1ntroduced into a still indicated at 10 in the drawing and heated in the usual way to effeet distillation, the vapors leaving the still through vapor off-take 11 and entering the base of a dephlegmating ractionating tower or column 12 packed with a de-chlorinating metal Y13 in granular or other fragmentary form so that the mass is permeable by the oil vapors. Zinc is an especially eiective dechlorinating metal to employ in the column. High-boiling constituents of the vapors condense and may either be returned to the still through run-back line 12a or directed elsewhere. The remaining hot oil vapors pass up through the mass of zinc and then leave the purifying tower through pipe 14 which conveys the puried vapors to a condenser 15 where gasoline condenses as a liquid and passes. through look-box 16 and line li to a suitable run-down tank. The zinc favors elimination of chlorine and assists in effecting'stabilization of the unsaturates and in the removal of sulfur. Sulfur is also removed by the zinc. The purified gasoline thus obtained may advantageously receive an alkaline wash, as with caustic soda s olution, to remove any traces of free chlorin that may be present, afterl which it is marketable as finished gasoline. The product possess good color and odor, gives a negative' test with doctor solution and is substantially stable.

The foregoing method of treatment may be modified to advantage in many cases by ensuring the presence of an added hydrogenating gas or vapor (the term gas being used generically to include either gas or vapor or both) in mixture with the vapors of the oil distilled from still 10 and passino' through the packed column 12. To this end natural gas, most desirably preheated, for example, may be introduced into the still through inlet 18 during the distillation, the hot mixture of oil vapors and natural gas then passing through the packed column where the zinc acts to remove chlorin from the chlorinated gasoline while the resulting nascent unsaturated hydrocarbons react, to-

' gether with the methane and other constituents of the natural gas, to form saturated compounds.

In some cases it is ffound advisable to supnly additional heat to the vapors passing through the mass of dechlorinating material in the dephlegmating tower 12. Thus, in re- {ining some types of crude distillates in acc ordance with the invention, light vapors distll over at temperatures insuiicicntlv high for most effective action of the de-chlorinating agent employed in the tower. Accordingly said tower may advantageously be provided w1th suitable heating means of appropriate character for raising the temperature of the vapors in the tower when this is necessary or advisable. In the present example such heating means is shown as comprising a jacket or housing 18 through which a heating medium, such as hot furnace or flue gases, for instance, may be passed.

While, in the specific example described hereinabove, the chlorinated oil is exposed in vapor form to the action of the de-chlorinating metal, it is feasible to place the de- 'chlorinating metal in the still with the chlorinated oil to be reined, and then to distil either with or without introducing natural gas or other hydrogenating gas into the still.

Where necessary or advisable, the resultant distillation vapors may also be subjected to the action of a de-chlorinating agent to remove residual chlorine.

VVhat is claimed is:

1. The process of refining mineral oils containing unsaturates ywhich comprises chlorinating such a mineral oil, and subjecting the chlorinated oil to heat in the presence of zinc. l

2. The process of refining mineral oils containing unsaturates which comprises chlorinating such a mineral oil, distillin the chlorinated oil, and contacting the hot istillation vapors with zinc.

The process of refining mineral oils containing unsaturates which comprises chlo'- rinating such a mineral oil, and subjecting the chlorinated oil to heat in the presence of zinc and a gaseous hydrogenating agent.

4. The process of refining mineral oils containing unsaturates which comprises chlorinating such a mineral oil, distilling the chlorinated oil, and subjecting the hot distillation vapors in mixture with a gaseous hydrogenating agent to the action of zincz 5. The process of refining a cracked -mlneral oil distillate which comprises chlorinati ng such a distillate, and subjecting the chlorinated distillate to heat in the presence of zinc.

6. The process of refining a cracked mineral oil distillate which com rises chlorinating such a distillate, and subjecting the chlorinated distillate to heat in the presence 'of zinc and a gaseous hydrogenating agent.

7. The process of refining crude gasoline containing unsaturates. which comprlses passing chlorine into such gasoline, and sub-A jecting the thus treated the presence of zine. i 8. The process of refining crude gasollne gasoline to heat in containing unsaturates which comprises passing chlorine into such gasoline until suiicient chlorination is eiective, distilling the thus treated gasoline, passing the hot distillation vapors through a permeable mass of Zinc, and condensing gasoline from the eiiiuent vapors.

9.V The process of refining crude gasollne containing unsaturates which comprises passing chlorine into such gasoline until the color thereof darkens, distilling the thus treated gasoline, passing the hot distillation vapors in company with an added hydrogenatin gas through a permeable mass of zinc, an condensing gasoline from the eluent vapors.

10. The process of 'refining crude gasoline containing unsaturates which comprises passing chlorine into such gasoline until the color thereof darkens, distilling the thus treated gasoline, passing the hot distillation vapors in company with natural gas through a permeable mass of zinc, and condensing gasoline from the eliuent vapors.

11. The process of reining mineral oils containing unsaturates which comprises chlorinating such a mineral oil, and thereafter subjecting the chlorinated oil to heat n the presence of a metallic de-chlorinating agent comprising zinc.

12. The process of refining mineral oils containing unsaturates which com rises chlorinating such a mineral oil, and distllling the chlorinated oil in the presence of a metallic de-chlorinatin agent comprising zinc.

13. The process o refining unstable mineral oils which comprises passing chlorine into such a mineral oil, distilling the oil in the presence of a metallic agent comprising zinc, and subjecting the resultant distillate to an alkaline Wash to remove residual traces of free chlorine.

14. The process of refining cracked mineral oil distillates to stabilize the same which comprises passing chlorine into such a distillate, redistilling said distillate in the presence of a metalllc agent comprising zinc, and subjecting the resultant distillate to an alkaline Wash to remove residual traces of free chlorine.

In testimony `whereof I hereunto affix my MORRIS TEPLITZ.

v signature. 

